Journal
ORGANOMETALLICS
Volume 25, Issue 10, Pages 2505-2513Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om051065j
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Mononuclear iridium(III) complexes of general formula IrX(H)(O2CR)[(S)-binap] (2, R = CH3; 3, R = Ph; 4, R = C6H4CH3-p; a, X = Cl; b, X = Br; c, X = 1) were prepared by one-pot reaction of [Ir(mu-X)(cod)12 with 2 equiv of (S)-BINAP [=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl] and an excess of the corresponding carboxylic acid in toluene. The structure of (S)-2-4 bearing an (S)-BINAP was confirmed to be OC-6-23-A (Lambda-conformation) by X-ray analysis of (S)4a-c. In this reaction, the iridium(1) complex (I) {Ir(mu-Cl)[(S)-binap]}(2) [(S)-5a] and pentacoordinated iridium(l) complexes IrX(cod)[(S)-binap] [(S)-7b, X = Br; (S)-7c, X = I] were generated prior to the oxidative addition of carboxylic acid. Cationic inuclear iridium(III) complexes of general formula [{Ir(H)[(S)-binap]}(2) (mu-X)(3)]X [(S)-8: a, X = Cl; b, X = Br; c, X = 1] were prepared, and their cationic bifacial octahedral dinuclear structure was characterized by spectral data and combustion analysis. The anionic portion of these complexes could be replaced by NaPF6, leading to the corresponding PF6 salts [{Ir(H)[(S)-binap]}(2)(mu-X)(3)]PF6 [(S)-8: d, X = Cl; e, X = Br; f, X = I]. Iodo-acetate complexes of p-TolBINAP (=2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl) [(S)-9c] and SYNPHOS [=2,2',3,3'-tetrahydro(5,5'-bi-1,4-benzodioxin)-6,6'-diyl]bis(diphenylphosphine)] [(S)40c] were also prepared according to the method used for the BINAP complex (S)-2c and were characterized spectroscopically. Cationic dinuclear complexes of p-TolBINAP [(S)-11c] and SYNPHOS [(S)-12c] were also generated. Using these complexes, the effect of halide variation was studied by asymmetric hydrogenation of 2-phenylpyrrolidine (13) and 2-phenyl-4,5,6,7-tetrahydro-3H-azepine (15) along with 2-phenylquinoline (16), and the results indicated that iodide complexes were better catalyst precursors for catalytic activity than the corresponding chloride and bromide complexes, but were not superior in enantioselectivity.
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